Synthesis, Structure, Spectroscopy, and Reactivity of a Neutral Iridathiabenzene

John R. Bleeke; and Paul V. Hinkle; Monica Shokeen; Nigam P. Rath

doi:10.1021/OM0400649

Synthesis, Structure, Spectroscopy, and Reactivity of a Neutral Iridathiabenzene

John R. Bleeke, and Paul V. Hinkle, Monica Shokeen, Nigam P. Rath

University of Missouri-St. Louis

Research output: Contribution to journal › Article › peer-review

Abstract

<div class="line" id="line-11"> Treatment of the cationic iridathiabenzene  <img src="https://pubs.acs.org/na101/home/literatum/publisher/achs/journals/content/orgnd7/2004/orgnd7.2004.23.issue-17/om0400649/production/images/medium/om0400649a10001.gif"/>  (3) with sodium  tert -butylthiolate leads to the production of a stable neutral iridathiabenzene,  <img src="https://pubs.acs.org/na101/home/literatum/publisher/achs/journals/content/orgnd7/2004/orgnd7.2004.23.issue-17/om0400649/production/images/medium/om0400649a10002.gif"/>  (4). Compound 4 exists in solution as an equilibrating mixture of two square pyramidal isomers, “ cis ” 4a and “ trans ” 4b. When 4 is cooled to −30 °C in acetonitrile, it precipitates as an acetonitrile adduct,  <img src="https://pubs.acs.org/na101/home/literatum/publisher/achs/journals/content/orgnd7/2004/orgnd7.2004.23.issue-17/om0400649/production/images/medium/om0400649a10003.gif"/>  (6), featuring an iridathiacyclohexa-1,3-diene ring system. Compound 6 reverts back to 4 upon redissolving and warming to room temperature. Treatment of 4 (or 6) with excess PMe 3  results in addition of PMe 3  to the iridium center and replacement of the bulky PEt 3  ligands with PMe 3 's, producing  <img src="https://pubs.acs.org/na101/home/literatum/publisher/achs/journals/content/orgnd7/2004/orgnd7.2004.23.issue-17/om0400649/production/images/medium/om0400649a10004.gif"/>  (7) as a mixture of equilibrating isomers, “ cis ” 7a and “ trans ” 7b. Compound 7, like 6, includes a nonaromatic iridathiacyclohexa-1,3-diene ring. When 4 in acetonitrile solvent (or 6) is reacted with trifluoromethanesulfonic acid, protonation occurs at the thiolate sulfur, causing loss of thiol. The resulting cationic fragment dimerizes to produce  <img src="https://pubs.acs.org/na101/home/literatum/publisher/achs/journals/content/orgnd7/2004/orgnd7.2004.23.issue-17/om0400649/production/images/medium/om0400649a10005.gif"/>  (8), in which the two iridium centers are bridged by the two ring sulfurs. Finally, treatment of 4 (or 6) with [(η 5 -C 5 Me 5 )Ru(NCMe) 3 ] + O 3 SCF 3-  results in production of the sandwich compound  <img src="https://pubs.acs.org/na101/home/literatum/publisher/achs/journals/content/orgnd7/2004/orgnd7.2004.23.issue-17/om0400649/production/images/medium/om0400649a10006.gif"/>  (9), which exists in solution as an equilibrating mixture of isomers, “ cis ” 9a and “ trans ” 9b. Compounds 4a, 7a, 8, and 9a have been structurally characterized by X-ray diffraction. </div>

Original language	American English
Journal	Organometallics
Volume	23
DOIs	https://doi.org/10.1021/OM0400649
State	Published - Jul 22 2004

Keywords

Synthesis
Structure
Spectroscopy
Reactivity of a Neutral Iridathiabenzene
Sulfur
Ligands
Group 15 compounds
Molecular structure
Transition metals

Disciplines

Organic Chemistry
Polymer Chemistry
Chemistry
Life Sciences
Biochemistry, Biophysics, and Structural Biology
Biochemistry

Access to Document

10.1021/OM0400649License: Unspecified

Cite this

@article{a72b080766864a62ad531f609cfcd730,

title = "Synthesis, Structure, Spectroscopy, and Reactivity of a Neutral Iridathiabenzene",

abstract = " Treatment of the cationic iridathiabenzene   (3) with sodium  tert -butylthiolate leads to the production of a stable neutral iridathiabenzene,   (4). Compound 4 exists in solution as an equilibrating mixture of two square pyramidal isomers, “ cis ” 4a and “ trans ” 4b. When 4 is cooled to −30 °C in acetonitrile, it precipitates as an acetonitrile adduct,   (6), featuring an iridathiacyclohexa-1,3-diene ring system. Compound 6 reverts back to 4 upon redissolving and warming to room temperature. Treatment of 4 (or 6) with excess PMe 3  results in addition of PMe 3  to the iridium center and replacement of the bulky PEt 3  ligands with PMe 3 's, producing   (7) as a mixture of equilibrating isomers, “ cis ” 7a and “ trans ” 7b. Compound 7, like 6, includes a nonaromatic iridathiacyclohexa-1,3-diene ring. When 4 in acetonitrile solvent (or 6) is reacted with trifluoromethanesulfonic acid, protonation occurs at the thiolate sulfur, causing loss of thiol. The resulting cationic fragment dimerizes to produce   (8), in which the two iridium centers are bridged by the two ring sulfurs. Finally, treatment of 4 (or 6) with [(η 5 -C 5 Me 5 )Ru(NCMe) 3 ] + O 3 SCF 3-  results in production of the sandwich compound   (9), which exists in solution as an equilibrating mixture of isomers, “ cis ” 9a and “ trans ” 9b. Compounds 4a, 7a, 8, and 9a have been structurally characterized by X-ray diffraction. ",

keywords = "Synthesis, Structure, Spectroscopy, Reactivity of a Neutral Iridathiabenzene, Sulfur, Ligands, Group 15 compounds, Molecular structure, Transition metals",

author = "Bleeke, {John R.} and Hinkle, {and Paul V.} and Monica Shokeen and Rath, {Nigam P.}",

note = "Treatment of the cationic iridathiabenzene (3) with sodium tert-butylthiolate leads to the production of a stable neutral iridathiabenzene, (4). Compound 4 exists in solution as an equilibrating mixture of two square pyramidal isomers, {"}cis{"} 4a and {"}trans{"} 4b. When 4 is cooled to −30 °C in acetonitrile, it precipitates as an acetonitrile adduct, (6), featuring an iridathiacyclohexa-1,3-diene ring system.",

year = "2004",

month = jul,

day = "22",

doi = "10.1021/OM0400649",

language = "American English",

volume = "23",

journal = "Organometallics",

}

TY - JOUR

T1 - Synthesis, Structure, Spectroscopy, and Reactivity of a Neutral Iridathiabenzene

AU - Bleeke, John R.

AU - Hinkle, and Paul V.

AU - Shokeen, Monica

AU - Rath, Nigam P.

N1 - Treatment of the cationic iridathiabenzene (3) with sodium tert-butylthiolate leads to the production of a stable neutral iridathiabenzene, (4). Compound 4 exists in solution as an equilibrating mixture of two square pyramidal isomers, "cis" 4a and "trans" 4b. When 4 is cooled to −30 °C in acetonitrile, it precipitates as an acetonitrile adduct, (6), featuring an iridathiacyclohexa-1,3-diene ring system.

PY - 2004/7/22

Y1 - 2004/7/22

N2 - Treatment of the cationic iridathiabenzene   (3) with sodium  tert -butylthiolate leads to the production of a stable neutral iridathiabenzene,   (4). Compound 4 exists in solution as an equilibrating mixture of two square pyramidal isomers, “ cis ” 4a and “ trans ” 4b. When 4 is cooled to −30 °C in acetonitrile, it precipitates as an acetonitrile adduct,   (6), featuring an iridathiacyclohexa-1,3-diene ring system. Compound 6 reverts back to 4 upon redissolving and warming to room temperature. Treatment of 4 (or 6) with excess PMe 3  results in addition of PMe 3  to the iridium center and replacement of the bulky PEt 3  ligands with PMe 3 's, producing   (7) as a mixture of equilibrating isomers, “ cis ” 7a and “ trans ” 7b. Compound 7, like 6, includes a nonaromatic iridathiacyclohexa-1,3-diene ring. When 4 in acetonitrile solvent (or 6) is reacted with trifluoromethanesulfonic acid, protonation occurs at the thiolate sulfur, causing loss of thiol. The resulting cationic fragment dimerizes to produce   (8), in which the two iridium centers are bridged by the two ring sulfurs. Finally, treatment of 4 (or 6) with [(η 5 -C 5 Me 5 )Ru(NCMe) 3 ] + O 3 SCF 3-  results in production of the sandwich compound   (9), which exists in solution as an equilibrating mixture of isomers, “ cis ” 9a and “ trans ” 9b. Compounds 4a, 7a, 8, and 9a have been structurally characterized by X-ray diffraction.

AB - Treatment of the cationic iridathiabenzene   (3) with sodium  tert -butylthiolate leads to the production of a stable neutral iridathiabenzene,   (4). Compound 4 exists in solution as an equilibrating mixture of two square pyramidal isomers, “ cis ” 4a and “ trans ” 4b. When 4 is cooled to −30 °C in acetonitrile, it precipitates as an acetonitrile adduct,   (6), featuring an iridathiacyclohexa-1,3-diene ring system. Compound 6 reverts back to 4 upon redissolving and warming to room temperature. Treatment of 4 (or 6) with excess PMe 3  results in addition of PMe 3  to the iridium center and replacement of the bulky PEt 3  ligands with PMe 3 's, producing   (7) as a mixture of equilibrating isomers, “ cis ” 7a and “ trans ” 7b. Compound 7, like 6, includes a nonaromatic iridathiacyclohexa-1,3-diene ring. When 4 in acetonitrile solvent (or 6) is reacted with trifluoromethanesulfonic acid, protonation occurs at the thiolate sulfur, causing loss of thiol. The resulting cationic fragment dimerizes to produce   (8), in which the two iridium centers are bridged by the two ring sulfurs. Finally, treatment of 4 (or 6) with [(η 5 -C 5 Me 5 )Ru(NCMe) 3 ] + O 3 SCF 3-  results in production of the sandwich compound   (9), which exists in solution as an equilibrating mixture of isomers, “ cis ” 9a and “ trans ” 9b. Compounds 4a, 7a, 8, and 9a have been structurally characterized by X-ray diffraction.

KW - Synthesis

KW - Structure

KW - Spectroscopy

KW - Reactivity of a Neutral Iridathiabenzene

KW - Sulfur

KW - Ligands

KW - Group 15 compounds

KW - Molecular structure

KW - Transition metals

UR - https://doi.org/10.1021/om0400649

U2 - 10.1021/OM0400649

DO - 10.1021/OM0400649

M3 - Article

VL - 23

JO - Organometallics

JF - Organometallics

ER -

Synthesis, Structure, Spectroscopy, and Reactivity of a Neutral Iridathiabenzene

Abstract

Keywords

Disciplines

Access to Document

Other files and links

Cite this